TW201431870A - Flame retardant for resin, flame retardant resin composition containing the same, and method for producing organic phosphorus compound - Google Patents

Abstract

A flame retardant for a resin containing an organophosphorus compound represented by the formula (I): (wherein R1, R2, R3 and R4 are each independently, and are an alkyl group having 1 to 8 carbon atoms or a haloalkyl group. , Z1 and Z2 are each independently a hydrogen atom, a methyl group or an ethyl group, and n is 0 to 10), and when the above organophosphorus compound is measured by gel permeation chromatography (GPC), the above formula (I) The compound content of n=0 is 0.1 to 3.0 area%, and the average degree of condensation (N) calculated from the content of each compound of n=0 to 10 in the above formula (I) is 1.5 to 3.5.

Description

Flame retardant for resin, flame retardant resin composition containing the same, and method for producing organic phosphorus compound Field of invention

The present invention relates to a flame retardant for a resin, a flame retardant resin composition containing the same, and a method for producing an organic phosphorus compound. More specifically, the present invention relates to a flame retardant for a resin, particularly a resin containing a volatile organic compound (VOC) and a polyphosphonate phosphate-based organophosphorus compound having a low molecular weight monomer type compound as a main component. A flame retardant which exhibits excellent flame retardancy as an additive-type flame retardant used for flame-retarding a polyurethane foam, and which has little change in duration and anti-fog property (low The present invention relates to a flame-retardant resin composition containing the above-mentioned flame retardant for a resin and a method for producing an organic phosphorus compound.

Background of the invention

In order to impart flame retardancy to the resin, a method of adding a flame retardant at the time of preparing a resin molded article can be employed. As the flame retardant, an inorganic compound, an organic phosphorus compound, an organic halogen compound, a halogen-containing organic phosphorus compound, or the like is known, and an organic halogen compound and a halogen-containing organic phosphorus compound exert an excellent flame retarding effect. Most of the flame retardants capable of obtaining a good flame retardant effect are organic phosphorus compounds, especially organic phosphates, halogen-containing organic phosphates.

For example, Japanese Patent Publication No. 3192242 (Patent Document 1), JP-A-49-43272 (Patent Document 2), and JP-A-56-36512 (Japanese Patent Publication No. Hei 56-36512) Patent Document 3) and Japanese Patent Laid-Open No. Hei 11-100391 (Patent Publication No. 4) and the like.

Among the various resins, the foam of the polyurethane resin (polyurethane foam) has flammability, so its use is limited, and in recent years, in order to block the polyurethane foam Combustion, various studies have been carried out, but still not enough.

In general, a flame retardant for a polyurethane foam is required to satisfy various conditions as described below.

(1) No coking will occur (foaming of foam)

(2) Sustainability of flame retardancy of foam

(3) The viscosity is moderate

(4) Good mixing of the foam components

(5) difficult to hydrolyze

(6) Reduce smoke or poison gas

(7) Does not deteriorate the physical properties of the foam

(8) Excellent anti-fogging property

(9) VOC, low molecular weight haplotype compounds

Among the above-mentioned conditions, the polyurethane foam is particularly required to have no coking, good flame retardancy, little physical property deterioration, excellent antifogging property, and few VOC and low molecular weight monomer compounds. In particular, in recent years, demands for antifogging properties, VOC, and low molecular weight monomeric compounds have been increasing.

In the past, flame retardants for polyurethane foams were used. Reference (2-chloroethyl) phosphate, ginseng (chloropropyl) phosphate, ginseng (dichloropropyl) phosphate, ginseng (2,3-dibromopropyl) phosphate, and the like.

When an organophosphorus compound such as ginseng (2-chloroethyl) phosphate and ginseng (dichloropropyl) phosphate is blended in a polyurethane foam, the flame retardant effect is exhibited initially. However, there is a problem that the effect is changed from time to time, and the flame retarding effect is remarkably lowered, and the antifogging property is poor, and the VOC and the low molecular weight monomer type compound are many. This is considered to be because the molecular weight of these organophosphorus compounds is small and the flame retardant is volatilized.

In addition, the flame retardancy of ginseng (2,3-dibromopropyl) phosphate and its The continuity is excellent, but the heat resistance is poor. When it is added to the polyurethane foam, coking occurs during the production of the foam, which is not suitable.

In addition, ginseng (2,3-dibromopropyl) phosphate has also been used as a flame retardant for polyester fibers, but it has carcinogenic concerns and is therefore not used now.

In recent years, a compound having two phosphorus atoms in one molecule, 2,2-bis(chloromethyl)trimethylenebis(bis(2-chloroethyl)phosphate) (refer to Patent Document 1) and 肆(2) -Chloroethyl)ethylene diphosphate (refer to Patent Document 2) can be gradually attracting attention as a flame retardant for polyurethane foam. However, these compounds are insufficient in flame retardancy and sustainability, and chlorine must be used in the production, which may cause problems at the manufacturing level.

Therefore, in order to improve these shortcomings, there are literatures discussing bis(2-chloroethoxy)phosphinyl (dimethyl)methyl]phosphate, 2-chloroethyl bis[bis(2-chloroethoxy) ) phosphinyl (dimethyl)methyl] phosphate (see Patent Documents 3 and 4).

However, these compounds contain a number of sub-generated ginseng in the manufacturing steps. A phosphorus compound monomer such as (2-chloroethyl) phosphate does not sufficiently satisfy the requirements of antifogging property, VOC, and a low molecular weight haplotype compound, and it is desired to develop a halogen-containing organophosphorus compound which satisfies requirements. And its manufacturing method.

Prior technical literature Patent literature

Patent Document 1: US Patent No. 3192242

Patent Document 2: Japanese Patent Publication No. Sho 49-43272

Patent Document 3: Japanese Patent Laid-Open No. 56-36512

Patent Document 4: Japanese Patent Laid-Open No. Hei 11-100391

Summary of invention

An object of the present invention is to provide a flame retardant for a resin, in particular, a flame retardant for a resin containing a polyphosphonate phosphate-based organophosphorus compound having a small amount of VOC and a low molecular weight monomer compound as a main component. The additive type flame retardant used in the flame retardation of the urethane foam exhibits excellent flame retardancy, and has little change in durability in a time-dependent manner, and is excellent in antifogging property. The present invention also provides a resistor comprising the foregoing resin. A flame retardant resin composition of a fuel and a method for producing an organic phosphorus compound.

The inventors of the present invention have repeatedly studied in order to solve the above problems, and as a result, found that a polyphosphonate phosphate type organophosphorus compound which lowers the content of a low molecular weight monomer type compound, that is, a phosphate monomer, can satisfy most of the resins. In particular, each required for a flame retardant for polyurethane foam The condition is an excellent flame retardant; and the method for producing the organophosphorus compound is found, and the present invention is completed.

In this way, according to the present invention, a flame retardant for a resin containing the organophosphorus compound represented by the general formula (I) can be provided:

(wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently an alkyl group having 1 to 8 carbon atoms or a haloalkyl group, and Z ₁ and Z ₂ are each independently a hydrogen atom, a methyl group or an ethyl group; n is 0 to 10), and when the organophosphorus compound is measured by gel permeation chromatography (GPC), the content of the compound of n=0 in the above formula (I) is 0.1 to 3.0 area%, and The average condensation degree (N) calculated from the content of each compound of n=0 to 10 in the formula (I) is from 1.5 to 3.5.

Further, according to the present invention, there can be provided a flame-retardant resin composition comprising the above-mentioned flame retardant for a resin and a resin.

Further, according to the present invention, there is provided a process for producing an organophosphorus compound which comprises the step of: (1) a compound represented by the formula (a) and a compound represented by the formula (b) ( b) and the compound (c) represented by the formula (c), in a ratio of 1.5 to 3.5 moles relative to the compound (a) 1 mol of the compound (c), further with respect to the aforementioned compound (c) 1 moles of the compound (b) is a ratio of 1.3 to 2.0 moles, and is reacted at a temperature of -20 to 60 ° C to obtain a compound (d) represented by the formula (d):

(wherein R ₁ and R _{2 have the} same meaning as in the formula (I), and R ₅ is an alkyl group having 1 to 8 carbon atoms or a haloalkyl group),

(wherein, Z ₁ and Z _{2 are} synonymous with the formula (I)),

(wherein R ₃ and R _{4 have the} same meaning as in the formula (I), and X is a halogen atom),

Wherein R ₁ , R ₂ , R ₃ , R ₄ , Z ₁ , Z ₂ and n are synonymous with the formula (I); and the step (2) is followed by the oxidizing agent obtained in the above step (1) The compound (d) is oxidized to obtain an organophosphorus compound represented by the above formula (I), and when the organophosphorus compound is measured by GPC, the content of the compound of n =0 in the above formula (I) is 0.1 to 3.0. The area%, and the average degree of condensation (N) calculated from the content of each compound of n = 0 to 10 in the above formula (I) is from 1.5 to 3.5.

According to the present invention, a flame retardant for a resin, in particular, a flame retardant for a resin containing a VOC and a polyphosphonate phosphate-based organophosphorus compound having a low VMW content and a low molecular weight monomer type compound as a main component, can be provided as a polyamine. The additive type flame retardant used in the flame retardation of the ethyl formate foam exhibits excellent flame retardancy, and has little change in durability in a time-dependent manner, and is excellent in antifogging property. The present invention also provides a flame retardant comprising the foregoing resin. A flame retardant resin composition of the agent and a method for producing the organophosphorus compound.

In the flame retardant for a resin of the present invention, the organophosphorus compound of the formula (I) having a main component has a very low volatility, and is added to the resin, in particular, a polyurethane before the foaming according to a predetermined formulation. Among the ester foam components, an excellent flame retarding effect can be exhibited. When the obtained polyurethane foam is measured in accordance with the flammability test method such as MVSS-302, it will exhibit excellent flame retardancy and antifogging property (low volatility), and the volatile component is extremely small.

The flame retardant for a resin of the present invention further exerts the above effects when any of the following conditions is satisfied: When the organophosphorus compound is determined by GPC, the content of the compound of n=1 in the general formula (I) is 10 to 50% by area, and. The average degree of condensation (N) in the formula (I) is from 1.8 to 3.0.

Further, the flame-retardant resin composition of the present invention further exerts the above effects when any of the following conditions is satisfied: . The resin is selected from the group consisting of polyurethane resin, acrylic resin, phenol resin, epoxy resin, vinyl chloride resin, polyamide resin, polyester resin, unsaturated polyester resin, styrene resin and synthetic rubber resin, especially Is a polyurethane resin is a polyurethane foam, and The flame retardant for a resin is contained in an amount of 1 to 40 parts by weight based on 100 parts by weight of the resin.

Further, when the method for producing an organophosphorus compound of the present invention satisfies any of the following conditions, the above effects are further exerted: When the organophosphorus compound is determined by GPC, the content of the compound of n=1 in the general formula (I) is 10 to 50% by area, and. The average degree of condensation (N) in the formula (I) is from 1.8 to 3.0.

Fig. 1 is a graph showing the flame retardancy of the flame retardant for a resin of the present invention.

Fig. 2 is a graph showing the phosphorus atom content retention ratio of the flame retardant for a resin of the present invention.

Form for implementing the invention

The flame retardant for a resin of the present invention contains an organophosphorus compound represented by the formula (I):

(wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently an alkyl group having 1 to 8 carbon atoms or a haloalkyl group, and Z ₁ and Z ₂ are each independently a hydrogen atom, a methyl group or an ethyl group; n is 0 to 10), characterized in that, when the organophosphorus compound is measured by gel permeation chromatography (GPC), the content of the compound of n=0 in the above formula (I) is 0.1 to 3.0 area%, and The average degree of condensation (N) calculated from the content of each compound of n = 0 to 10 in the above formula (I) is from 1.5 to 3.5.

In addition, in the present invention, "A to B" indicating a numerical range means A or more and B or less.

In the following, the organic phosphorus compound (hereinafter also referred to as "organophosphorus compound (I)") and [2] organophosphorus compound (I) represented by the formula (I) contained in the flame retardant for a resin of the present invention. The manufacturing method of [3] and the order of the flame-retardant resin composition of this invention are demonstrated.

[1]Organic phosphorus compounds (I)

The organophosphorus compound (I) contained in the flame retardant for a resin of the present invention can be represented by the formula (I).

The substituents R ₁ , R ₂ , R ₃ and R ₄ in the formula (I) are each independently, and are an alkyl group having 1 to 8 carbon atoms or a haloalkyl group, an alkyl group having 1 to 4 carbon atoms or a haloalkyl group. Preferably, a haloalkyl group having 1 to 4 carbon atoms is more preferred.

The halogen atom of the haloalkyl group may, for example, be fluorine, chlorine, bromine or iodine, preferably chlorine or bromine, and particularly preferably chlorine.

Specific examples of the substituent include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group, cyclohexyl group, n-octyl group, isooctyl group, and 2- An alkyl group such as ethylhexyl: chloromethyl, chloroethyl, chloropropyl, chloroisopropyl, dichloropropyl, dichloroisopropyl, chlorobutyl, dichlorobutyl, dichloroisobutyl , bromomethyl, bromoethyl, bromopropyl, bromoisopropyl, dibromopropyl, dibromoisopropyl, bromobutyl, dibromobutyl, dibromoisobutyl, bromochloropropyl, bromine a haloalkyl group such as chloroisopropyl, bromochlorobutyl or bromochloroisobutyl.

Among these, chloromethyl, chloroethyl, chloropropyl, chloroisopropyl, Dichloropropyl, dichloroisopropyl, chlorobutyl, dichlorobutyl, dichloroisobutyl, bromomethyl, bromoethyl, bromopropyl, bromoisopropyl, dibromopropyl, dibromo Isopropyl, bromobutyl, dibromobutyl, dibromoisobutyl, bromochloropropyl, bromochloroisopropyl, bromochlorobutyl, bromochloroisobutyl, etc. The base is preferably chloroethyl, chloropropyl, chloroisopropyl, dichloropropyl or dichloroisopropyl.

The substituents Z ₁ and Z ₂ in the formula (I) are each independently a hydrogen atom, a methyl group or an ethyl group.

The number n of repeating units in the general formula (I) is 0 to 10, which constitutes organic phosphating The compound of the component of the compound (1) is a mixture of compounds having n of 0 to 10. However, even if the values of n are different and the degree of condensation is different, the properties of the resin-based flame retardant are almost the same.

In this manner, n in the general formula (I) may be from 0 to 10. However, in consideration of the handleability of the flame retardant for a resin and the flame retardant resin composition or the effect obtained, the viscosity must be moderate.

In addition, in order to produce a flame retardant for resins having excellent antifogging property and a small amount of phosphate monomers, the n-based compound of the main component of the organophosphorus compound (I) is preferably 1 to 5, and 1 to 3 Either one is especially good.

The number of specific repeating units n is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10, and 1, 2, 3, 4, and 5 are preferred, and 1, 2, and 3 are Very good.

Here, the main component means the component having the highest content among the components constituting the organophosphorus compound (I).

Therefore, the organic phosphating contained in the flame retardant for a resin of the present invention When the compound (I) is measured by gel permeation chromatography (GPC: Gel Permeation Chromatography), the content of the compound of the formula (I) is 0.1 to 3.0 area%, and the formula is The average condensation degree (N) calculated by the content of each compound in (I) n = 0 to 10 is 1.5 to 3.5.

The specific compound content (area %) of n=0 is, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, and 3.0, etc.

The organophosphorus compound (I) does not contain the n=0 in the general formula (I) The compound, that is, the monomeric phosphate is preferred, however, in the production step, the compound of the formula (I) is n=0, and therefore, if it is 0.1 to 3.0 area% in the GPC measurement, It may also contain the compound.

Further, from the above reasons, in the GPC measurement, the content of the compound of n = 1 in the formula (I) is preferably 10 to 50% by area. The upper limit is preferably 45 area%, and more preferably 40 area%. Further, the lower limit is preferably 15 area%, more preferably 20 area%.

The specific compound content (area %) of n=1 is, for example, 10, 15, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 45 and 50, etc.

From the above, the average degree of condensation of the organophosphorus compound (I) (N) is 1.5 to 3.5. The upper limit is preferably 3.0. Further, the lower limit is preferably 1.8, and more preferably 2.0.

The specific average degree of condensation (N) is, for example, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4 and 3.5 and so on.

The average degree of condensation (N) is determined by the following formula using the GPC area fraction (A _n ) of each component of n = 0 to 10 in the GPC measurement.

N=Σ(n.A _n )/Σ(A _n )

The content of each compound (component) of n=0 to 10 of the organophosphorus compound (I) measured by GPC measurement can be analyzed (measured) by, for example, the following.

Specifically, 10 ml of tetrahydrofuran (THF) was added to 0.09 g of a sample by a full pipette to prepare a sample solution, which was analyzed by the following apparatus and analysis conditions, and the area % measured by the RI detector was used as each compound. Content (composition).

(machine)

GPC analyzer (manufactured by Tosoh Corporation, model: HLC-8220 or equivalent)

Data analysis device (manufactured by Tosoh Corporation, model: SC-8010 or equivalent)

(column)

Protection column

(made by Tosoh Corporation, model: TSKguardcolumn SuperHZ-L 4.6mmI.D.×2.0cm) 1

Sample column

(Dongcao Co., Ltd., model: TSKGEL SuperHZ1000 6.0mmI.D. × 15cm) 3

(Dongcao Co., Ltd., model: TSKGEL SuperHZ2000 6.0mmI.D. × 15cm) 1

(analysis conditions)

INLET temperature 40 ° C

Column temperature 40 ° C

RI temperature 35 ° C

Solvent flow rate 0.25ml/min

RI (Refractive Index: Refractive Index)

Sample solution injection amount 10μl (loop)

(data processing conditions)

START TIME (minutes) 25.00

STOP TIME (minutes) 50.00

The polyphosphonate phosphate type organophosphorus compound (I) of the present invention may be a compound having a combination of the above substituents and the number of repeating units, or a mixture having two or more kinds of different substituents.

Among these, a compound having n = 1 is, for example, 1-[bis(2-chloroethoxy)phosphinyl]-1-methylethylbis(2-chloroethyl)phosphate, and 1- [Bis(2-chloroethoxy)phosphinyl]ethyl bis(2-chloroethyl)phosphate; and such a condensate represented by n=2 or more is particularly preferable.

The polyphosphonate phosphate represented by the formula (I) of the present invention A flame retardant for a resin of a type organophosphorus compound can be used as a flame retardant for various resins.

Examples of the resin to be added include, for example, a polyurethane resin, an acrylic resin, a phenol resin, an epoxy resin, a vinyl chloride resin, a polyamide resin, a polyester resin, an unsaturated polyester resin, a styrene resin, and a synthesis. Rubber, etc. Among these, a polyurethane resin and an acrylic resin are preferred, a polyurethane resin is preferred, and a foam of a polyurethane resin, that is, a polyurethane foam is used. Very good.

Polyurethane foam can be soft, semi-rigid and hard Either the flame retardant of the present invention is suitably used as an additive type flame retardant for these foams.

Since the polyurethane foam has air-permeable continuous cells, the conventional flame retardant for resin may be volatilized and scattered, and the flame retardancy may be lowered or the function may be lost, so that the antifogging property is lowered. There are also problems with a large amount of phosphate monomers. In the flame retardant for a resin of the present invention, the volatile component is small, the flame retardancy is continuously exhibited, the antifogging property is improved, and the phosphate monomer can be reduced.

[2] Method for producing organophosphorus compound (I)

The organophosphorus compound (I) of the present invention can be produced, for example, by a well-known two-stage reaction under the conditions described later.

That is, the compound (d) can be obtained by reacting the compounds (a), (b) and (c) by the step (1), and then the step (1) is carried out by the oxidizing agent by the step (2). The obtained compound (d) is obtained by oxidation.

Steps (1) and (2) can theoretically be represented by the following reaction formulas (1) and (2), respectively. Shown (wherein OA represents an oxidizing agent).

The following describes each step.

step 1)

In the step (1), the compounds (a), (b) and (c) are further added to the compound (c) in a ratio of 1.5 to 3.5 mol relative to the compound (a) 1 molar compound (c). 1 mole of the compound (b) is a ratio of 1.3 to 2.0 moles, and the reaction is carried out at a temperature of -20 to 60 ° C to obtain a compound (d). That is, q=1.5~3.5, and p/q=1.3~2.0. RX is liberated by the reaction of the compounds (a), (b) and (c) (R is synonymous with R ₁ , R ₂ , R ₃ , R ₄ and R ₅ , and X is a halogen atom).

In the formula, "+OA" means the addition of an oxidizing agent.

Here, the reason why the value of the coefficient q is set to q=1.5 to 3.5 will be described.

The average degree of condensation (N) of the organophosphorus compound (I) of the present invention theoretically corresponds to the coefficient q in the reaction formula (1), and therefore, in order to make the average degree of condensation (N) within the range set by the present invention, The molar ratio corresponding to the ratio of the compounds (a), (b), and (c) may be used.

In the step (1), the coefficient q of the compound (c) must exceed 1.

This is because when the coefficient q is less than 1, the unreacted compound (a) is necessarily present, which becomes a source of the monomeric phosphate represented by the compound (d) and the formula (I).

Further, in the case where the coefficient q is 1, the monomeric phosphate represented by n=0 in the general formula (I) is not produced in the theoretical reaction formula, but in reality, the reaction rate may not be 100%, so in order to reduce The content of the monomeric phosphate represented by the compound (d) and the formula (I) wherein n = 0, the coefficient q must exceed 1.

Further, the reason why the value of the coefficient p is defined as the ratio of p to q, p/q = 1.3 to 2.0, will be described.

In the reaction of the step (1), the compound (b) is bonded between the compound (a) and the compound (c) to exhibit a function as a condensing agent. Therefore, in the theoretical reaction formula, the compound (b) and the compound (c) should produce the compound (d) in the same molar amount, but in reality, the reaction rate may not be 100%. Therefore, it is necessary to add the excess compound (b).

From the above, in order to allow the compounds (a), (b) and (c) to be condensed without leaving the unreacted compound (a) and the compound (c), the average degree of condensation (N) is 1.5~. 3.5, it is necessary to use the compound (c) in a ratio of 1.5 to 3.5 moles relative to the compound (a) 1 molar. That is q=1.5~3.5. The upper limit is preferably 3.0, and the lower limit is preferably 1.7. In addition, it must also be The compound (b) is used in a ratio of 1.3 to 2.0 mol per mol of the compound (c). That is, p/q=1.3~2.0. The upper limit is preferably 1.7, and the lower limit is preferably 1.4.

The value of the specific coefficient q is, for example, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, and 3.0.

Further, the ratio p/q of the value of the specific coefficient p to q is, for example, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, and 2.0.

The reaction temperature in the step (1) is -20 to 60 °C.

If the reaction temperature is lower than -20 ° C, the reaction may be slow and may not proceed sufficiently. On the other hand, when the reaction temperature is higher than 60 ° C, the reaction proceeds abruptly and becomes difficult to control. The lower limit of the reaction temperature is preferably -10 ° C, and 0 ° C is preferred. The upper limit is preferably 50 ° C, and 40 ° C is preferred.

The specific reaction temperature (° C.) is, for example, -20, -15, -10, -5, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, and the like.

Here, the substituents R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are all preferably the same.

In the case where all of the substituents are the same haloalkyl group, the compound (a) in the step (1) can be simultaneously prepared by adjusting the molar ratio of the corresponding alkylene oxide to the phosphorus trihalide and then reacting it. Phosphite and phosphorus halide of compound (c).

Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, trimethylene oxide, and tetramethylene oxide. Among these, ethylene oxide and propylene oxide are preferred, and ethylene oxide is particularly preferred.

By measuring the active halogen atom (X) in the reaction solution at this time, and calculating The X atom concentration of the compound (c) can be determined by the amount of the compound (b) required.

For example, when R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are a chloroethyl group and the active halogen atom is chlorine, the concentration of the active halogen atom is preferably 9 to 11% by weight, and 9 to 10% by weight is Preferably.

The concentration (% by weight) of the specific active halogen atom may, for example, be 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10.0, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8, 10.9 and 11.0, etc.

Next, the raw material compound of the step (1) will be explained.

The compound (a) can be represented by the following formula.

(wherein R ₁ and R _{2 have the} same meaning as in the formula (I), and R ₅ is an alkyl group having 1 to 8 carbon atoms or a haloalkyl group)

Examples of the alkyl group having 1 to 8 carbon atoms and the haloalkyl group of R ₅ include R ₁ and R ₂ exemplified in the formula (I).

Compound (a) is a trialkyl phosphite or a sulfhydryl (haloalkyl) phosphorous The acid ester can be produced, for example, by a known method as described in the specification of U.S. Patent No. 3,803,272. Specifically, it can be produced by a reaction of phosphorus trichloride with an alkanol or an alkylene oxide.

Specific examples of the compound (a) include trimethyl phosphite, and three Ethyl phosphite, methyl diethyl phosphite, dimethyl ethyl phosphite, tripropyl phosphite, methyl ethyl propyl phosphite, triisopropyl Phosphite, tributyl phosphite, triisobutyl phosphite, trihexyl phosphite, tricyclohexyl phosphite, tris(n-octyl) phosphite, tris(isooctyl)phosphoric acid Ester, tris(2-ethylhexyl) phosphite, ginseng (chloromethyl) phosphite, ginseng (chloroethyl) phosphite, chloromethyl bis(chloroethyl) phosphite, di(chloro Methyl)chloroethyl phosphite, ginseng (chloropropyl) phosphite, ginseng (dichloropropyl) phosphite, chloroethyl bis(chloropropyl) phosphite, di(chloroethyl) Chloropropyl phosphite, chloromethylchloroethyl chloropropyl phosphite, cis (chloroisopropyl) phosphite, chloroethyl bis(chloroisopropyl) phosphite, di(chloroethyl) Chloroisopropyl phosphite, chloromethylchloroethyl chloroisopropyl phosphite, ginseng (dichloroisopropyl) phosphite, ginseng (bromomethyl) phosphite, gin (bromoethyl) Phosphite, ginsyl (bromopropyl) phosphite, ginseng (dibromopropyl) phosphite, ginseng (bromoisopropyl) phosphite, ginseng (dibromoisopropyl) phosphite, ginseng (bromochloropropyl) phosphite, ginseng (bromochloroisopropyl) phosphite, etc. Phosphite, ginseng (chloropropyl) phosphite, ginseng (dichloropropyl) phosphite, ginseng (chloroisopropyl) phosphite, ginseng (dichloroisopropyl) phosphite good.

Compound (b) can be represented by the following formula.

(wherein Z ₁ and Z _{2 are} synonymous with formula (I))

Specific examples of the compound (b) include formaldehyde, acetaldehyde, ketone aldehyde, acetone, methyl ethyl ketone, diethyl ketone, etc., among which acetaldehyde and acetone are used. Methyl ethyl ketone is preferred, acetaldehyde and acetone are preferred, and acetone is particularly preferred.

Compound (c) can be represented by the following formula.

(wherein R ₃ and R _{4 have the} same meaning as in the formula (I), and X is a halogen atom)

Examples of the halogen atom X include fluorine, chlorine, bromine and iodine, and chlorine and bromine are preferred, and chlorine is particularly preferred.

Compound (c) is a dialkyl halogenated or di(haloalkyl) halogenated Phosphorus can be produced by stopping the reaction with a diester according to a known method as described in the specification of U.S. Patent No. 3,803,272, specifically, a phosphorus trihalide such as phosphorus trichloride or an alkanol can be obtained by a diester. Or the reaction of the alkylene oxide is stopped to be produced.

Specific examples of the compound (c) include dimethylphosphonium chloride and diethyl Phosphorus chloride, methyl ethylphosphonium chloride, dipropylphosphonium chloride, methylpropylphosphonium chloride, ethylpropylphosphonium chloride, diisopropylphosphonium chloride, ethylisopropyl chloride Phosphorus, dibutylphosphonium chloride, diisobutylphosphonium chloride, dihexylphosphonium chloride, dicyclohexylphosphonium chloride, di(n-octyl)phosphorus chloride, di(isooctyl)phosphorus chloride , bis(2-ethylhexyl)phosphine chloride, bis(chloromethyl)phosphine chloride, bis(chloroethyl)phosphorus chloride, chloromethylchloroethylphosphonium chloride, di(chloropropyl) chloride Phosphorus, chloroethyl chloropropylphosphine chloride, bis(dichloropropyl)phosphine chloride, bis(chloroisopropyl)phosphorus chloride, chloroethylchloroisopropylphosphonium chloride, di(dichlorochloride) Isopropyl)phosphorus chloride, bis(bromomethyl)phosphine chloride, bis(bromoethyl)phosphorus chloride, bis(bromopropyl)phosphorus chloride, bis(dibromopropyl)phosphorus chloride, two (bromoisopropyl)phosphorus chloride, bis(dibromoisopropyl)chlorination Phosphorus, bis(bromochloropropyl)phosphine chloride, bis(bromochloroisopropyl)phosphorus chloride, etc., among which are bis(chloroethyl)phosphoric chloride, di(chloropropyl)phosphoric chloride Further, bis(dichloropropyl)phosphine chloride, bis(chloroisopropyl)phosphorus chloride and bis(dichloroisopropyl)phosphorus chloride are particularly preferred.

Step (2)

In the step (2), the compound (d) obtained in the step (1) is oxidized with an oxidizing agent to obtain the organophosphorus compound (I) of the present invention. That is, in the step (2), the phosphite moiety of the compound (d) is oxidized.

Specific examples of the oxidizing agent include peracetic acid and hydrogen peroxide, and hydrogen peroxide is particularly preferred. Hydrogen peroxide can be used as an aqueous solution, particularly preferably 35 (weight/volume)% hydrogen peroxide water which is commonly used in industrial applications.

In the step (2), if necessary, an aqueous sodium hydroxide solution is appropriately added to the reaction liquid, and the pH of the reaction liquid may be maintained at 9.5 to 10.5 while hydrogen peroxide is dropped. The aqueous sodium hydroxide solution is preferably a 30 (weight/volume)% aqueous solution which is often used industrially.

Specific pH is, for example, 9.5, 9.6, 9.7, 9.8, 9.9, 10.0, 10.1, 10.2, 10.3, 10.4, and 10.5.

The reaction temperature in the step (2) is preferably 5 to 50 ° C, and the upper limit is preferably 40 ° C, and the lower limit is preferably 10 ° C.

The specific reaction temperature (° C.) is, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, and the like.

The above description of the method for producing the organophosphorus compound (I) of the present invention, and by selecting the type of the phosphite, the phosphorus halide, the aldehyde and the ketone of the main raw material of the reaction, a plurality of compounds can be produced, which are of course in the present invention. Within the scope of the Ming.

Further, the method for producing the organophosphorus compound (I) of the present invention has an advantage in that various organophosphorus compounds (I) can be produced by adjusting the phosphorus content, the halogen content, the molecular weight, and the like according to the purpose.

In actual production, the desired compound may be selected from these compounds, or a mixture of two or more compounds, or a mixture of different degrees of condensation. However, in order to achieve excellent antifogging properties, it is necessary to minimize the general formula. (I) The content of the monomeric phosphate represented by n=0.

[3] Flame retardant resin composition

The flame-retardant resin composition of the present invention is characterized by comprising the flame retardant for a resin of the present invention and a resin.

The resin is exemplified as the resin to be added to the flame retardant for the resin.

The flame-retardant resin composition of the present invention preferably contains 1 to 40 parts by weight of the flame retardant for the resin, based on 100 parts by weight of the resin. The amount of the flame retardant to be added to the resin may be appropriately set in accordance with the type of the resin, the degree of flame retardancy desired, and the like.

The specific amount (parts by weight) of the flame retardant for the resin relative to 100 parts by weight of the resin is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, and 14. 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 30, 35 and 40, etc.

In the flame-retardant resin composition using the organophosphorus compound of the present invention, a well-known resin additive, that is, other flame retardant or flame retardant may be contained in a range that does not adversely affect the physical properties of the resin. Other additives.

Other flame retardants include, for example, triphenyl phosphate and trimethylphenol. Non-halogen phosphate flame retardant such as phosphatidyl ester, cresyl diphenyl phosphate, resorcinol-tetraphenyl bisphosphate, bisphenol A-tetraphenyl bisphosphate; 2, 2 pairs (Chloromethyl)-1,3-propane bis(chloroethyl) diphosphate, hydrazine (2-chloroethyl) ethylene diphosphate, (poly)alkylene glycol halogen-containing polyphosphate, ginseng Halogen-containing phosphate ester flame retardant such as tribromo)nepentyl phosphate; bromine flame retardant such as decabromodiphenyl ether, tetrabromobisphenol A, 1,2-bis(pentabromophenyl)ethane An inorganic flame retardant such as antimony trioxide or magnesium hydroxide; a nitrogen-based flame retardant such as ammonium polyphosphate or melamine phosphate.

Other additives other than the flame retardant include antioxidants, fillers, lubricants, modifiers, perfumes, antibacterial agents, pigments, dyes, heat-resistant agents, weathering agents, antistatic agents, ultraviolet absorbers, stabilizers, and strengthening agents. , anti-drip agent, anti-blocking agent, wood powder, starch, etc.

The flame retardant for organophosphorus compound type resin of the invention is particularly suitable In combination with a polyurethane foam, a flame retardant resin composition containing the flame retardant for a resin of the present invention and a polyurethane foam, that is, a flame-retardant polyurethane foam The body has superior flame retardancy and durability as compared with the polyurethane foam which is flame-retarded by the existing organophosphorus compound-based flame retardant, and also has excellent anti-fogging property.

The production method of polyurethane foam is well known, and the addition of resistance The flame-retardant polyurethane foam of the fuel can also be produced by a known method.

For example, the flame retardant for resin represented by the general formula (I) of the present invention is mixed with 100 parts by weight of the polyol containing a polyester polyol, a polyether polyol or the like. ~30 parts by weight, preferably 3 to 20 parts by weight. Further, a foam stabilizer, a catalyst, a foaming agent, and the like are added to the obtained mixture, stirred, and then an organic polyisocyanate is added to cause a reaction to obtain a flame-retardant polyurethane foam.

The specific amount (parts by weight) of the specific flame retardant for the resin relative to 100 parts by weight of the polyol is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 15, 15, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, and 30.

Examples of the organic polyisocyanate include toluene diisocyanate and benzene. Diisocyanate, xylene diisocyanate, biphenyl diisocyanate, naphthalene diisocyanate, diphenylmethane diisocyanate, cyclopentane diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, norbornane diisocyanate, Sanya Methyl diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butene diisocyanate, 2,3-butene Isocyanate, 1,3-butene diisocyanate, and the like.

Example

The invention is further illustrated by the following examples and comparative examples, but the scope of the invention is not limited thereto.

[Example 1]

(Reaction step: step (1))

A flask having a stir bar, a thermometer, an intake pipe, and a condenser tube and having a capacity of 1000 ml was filled with 275 g (2.0 mol) of phosphorus trichloride, 0.55 g of triethylamine, and 0.65 g of vinyl chloride. Next, add the resulting mixture under agitation Heat to 40 ~ 50 ° C, the cylinder through the flow meter and the intake pipe takes 4 hours to fill 208g (4.72 moles) of ethylene oxide gas. Then, it is heated to 50 to 60 ° C for 1 hour (cooked) to obtain ginseng (2-chloroethyl) phosphite as compound (a) and bis(2-chloroethyl) chloride as compound (c). A mixture of phosphorus (0.70 moles and 1.30 moles, respectively). The active chlorine concentration of the reaction mixture was 9.6%.

The obtained reaction mixture was maintained at 0 to 10 ° C, and 1 mol of lithium bis(2-chloroethyl)phosphonate as the compound (c) was added, and 1.5 mol was added as a compound via a dropping funnel for 2 hours. (b) Acetone 113 g (1.95 mol). The reaction was allowed to proceed at the same temperature for 12 hours, and then the reaction temperature was slowly raised to cause a reaction at 30 to 40 ° C for 24 hours. The acid value of the reaction mixture was 2.2.

(Reaction step: step (2))

Then, the obtained reaction mixture containing the compound (d) was kept at 5 to 10 ° C, and 6 g of a 30% aqueous sodium hydroxide solution was added through a dropping funnel. The pH of the reaction mixture was 10.5.

Next, the obtained reaction mixture was kept at 10 to 20 ° C, and 71 g (0.73 mol) of a 35% aqueous hydrogen peroxide solution as an oxidizing agent was added over 4 hours. When an aqueous hydrogen peroxide solution was added, a 30% aqueous sodium hydroxide solution was appropriately added, and the pH was adjusted so that the pH of the reaction mixture became 9.5 to 10.5. The total amount of the 30% aqueous sodium hydroxide solution was 25 g. After the completion of the addition of the aqueous hydrogen peroxide solution, the temperature was maintained at 30 to 40 ° C, and the reaction was continued for 2 hours.

(post-processing steps)

10 g of a 30% aqueous sodium hydroxide solution was added to the obtained reaction mixture, and the mixture was heated to 40 to 50 ° C and stirred for 1 hour. Next, the obtained reaction mixture is placed in a separatory funnel to separate it into an aqueous phase and organic phase. The obtained organic phase was washed twice with 200 ml of warm water of 60 to 70 ° C, and then the low boiling component was removed under reduced pressure of 1 to 3 kPa and at 90 to 100 ° C. The obtained product was designated as Flame Retardant A.

As a result of analysis of the flame retardant A, it is understood that the main component is a formula of the formula (I) wherein R ₁ , R ₂ , R ₃ and R ₄ are 2-chloroethyl, Z ₁ and Z ₂ are methyl 1-[double (2-Chloroethoxy)phosphinyl]-1-methylethylbis(2-chloroethyl)phosphate.

As a result of GPC measurement, the compound of n = 0 was 0.9 area%, the compound of n = 1 was 37.2 area%, and the average degree of condensation (N) was 2.12.

In addition, the phosphorus content (P) is 13.8% by weight, the chlorine content (Cl) is 26.1% by weight, and the viscosity is 4320 mPa. s (25 ° C), acid value of 0.03 KOHmg / g.

[Embodiment 2]

A ginseng (2-chloroethyl)phosphoric acid as the compound (a) was obtained in the same manner as in Example 1 except that 208 g (4.72 mol) of ethylene oxide was changed to 206 g (4.70 mol). A mixture of an ester and bis(2-chloroethyl)phosphine chloride as the compound (c) (0.65 mol and 1.35 mol, respectively). The active chlorine concentration of the reaction mixture was 10.0%.

Further, the obtained reaction mixture was kept at 40 ° C instead of 0 to 10 ° C, and it took 6 hours via the dropping funnel with respect to 1 mol of bis(2-chloroethyl)phosphorus chloride as the compound (c). Instead of adding 1.5 mol of acetone (116 g) of the compound (b) in an amount of 1.5 hours, it was reacted at the same temperature for 12 hours, and 71 g (0.73 mol) of a 35% aqueous hydrogen peroxide solution as an oxidizing agent was changed to Flame Retardant B was obtained in the same manner as in Example 1 except 65 g (0.67 mol).

As a result of analysis of the flame retardant B, it is understood that the main component is _{1- 1} in the formula (I) wherein R ₁ , R ₂ , R ₃ and R ₄ are 2-chloroethyl, Z ₁ and Z ₂ are methyl. Bis(2-chloroethoxy)phosphinyl]-1-methylethylbis(2-chloroethyl)phosphate.

As a result of GPC measurement, the compound of n=0 was 0.5 area%, the compound of n=1 was 29.2 area%, and the average degree of condensation (N) was 2.41.

In addition, the phosphorus content (P) is 13.9% by weight, the chlorine content (Cl) is 24.8% by weight, and the viscosity is 6200 mPa. s (25 ° C), acid value of 0.05 KOHmg / g.

[Example 3]

A mixture of ginic acid (2-chloroethyl) phosphite and bis(2-chloroethyl)phosphine chloride was obtained in the same manner as in Example 1.

Further, the obtained reaction mixture was kept at 40 ° C instead of 0 to 10 ° C, and it took 6 hours via the dropping funnel with respect to 1 mol of bis(2-chloroethyl)phosphorus chloride as the compound (c). 1.7 m of acetone (128 g (2.20 mol)) of the compound (b) was not added over 2 hours, and the reaction was carried out at the same temperature for 12 hours, and 71 g (0.73 mol) of a 35% aqueous hydrogen peroxide solution as an oxidizing agent was changed to Flame retardant C was obtained in the same manner as in Example 1 except for 65 g (0.67 mol).

As a result of analysis of the flame retardant C, it is understood that the main component is _{1- 1} in the formula (I) wherein R ₁ , R ₂ , R ₃ and R ₄ are 2-chloroethyl, Z ₁ and Z ₂ are methyl. Bis(2-chloroethoxy)phosphinyl]-1-methylethylbis(2-chloroethyl)phosphate.

As a result of GPC measurement, the compound of n = 0 was 1.3 area%, the compound of n = 1 was 34.7 area%, and the average degree of condensation (N) was 2.16.

In addition, the phosphorus content (P) is 13.7% by weight, the chlorine content (Cl) is 25.1% by weight, and the viscosity is 2200 mPa. s (25 ° C), the acid value is 0.02 KOHmg / g.

[Example 4]

A ginseng (2-chloroethyl)phosphoric acid as the compound (a) was obtained in the same manner as in Example 1 except that 208 g (4.72 mol) of ethylene oxide was changed to 198 g (4.50 mol). A mixture of an ester and bis(2-chloroethyl)phosphorus chloride as compound (c) (0.59 moles and 1.40 moles, respectively). The active chlorine concentration of the reaction mixture was 10.5%.

Further, the obtained reaction mixture was kept at 40 ° C instead of 0 to 10 ° C, and it took 6 hours via the dropping funnel with respect to 1 mol of bis(2-chloroethyl)phosphorus chloride as the compound (c). Instead of adding 1.5 mol of acetone 123 g (2.12 mol) as the compound (b) in 2 hours, the reaction was carried out at the same temperature for 12 hours, and 71 g (0.73 mol) of a 35% aqueous hydrogen peroxide solution as an oxidizing agent was changed to Flame retardant D was obtained in the same manner as in Example 1 except 60 g (0.62 mol).

As a result of analysis of the flame retardant D, it is understood that the main component is _{1- 1} in the formula (I) wherein R ₁ , R ₂ , R ₃ and R ₄ are 2-chloroethyl, Z ₁ and Z ₂ are methyl. Bis(2-chloroethoxy)phosphinyl]-1-methylethylbis(2-chloroethyl)phosphate.

As a result of GPC measurement, the compound of n = 0 was 0.5 area%, the compound of n = 1 was 22.9 area%, and the average degree of condensation (N) was 2.70.

In addition, the phosphorus content (P) is 14.2% by weight, the chlorine content (Cl) is 24.5% by weight, and the viscosity is 7700 mPa. s (25 ° C), acid value of 0.05 KOHmg / g.

[Example 5]

A ginseng (2-chloroethyl)phosphoric acid as the compound (a) was obtained in the same manner as in Example 1 except that 208 g (4.72 mol) of ethylene oxide was changed to 206 g (4.70 mol). A mixture of an ester and bis(2-chloroethyl)phosphorus chloride as compound (c) (0.73 moles and 1.27 moles, respectively). Reaction mixture activity The chlorine concentration was 9.4%.

Further, the obtained reaction mixture was kept at 40 ° C instead of 0 to 10 ° C, and it took 6 hours via the dropping funnel with respect to 1 mol of bis(2-chloroethyl)phosphorus chloride as the compound (c). A flame retardant E was obtained in the same manner as in Example 1 except that 97 g of acetone (1.67 mol) of the compound (b) was added in an amount of 1.3 hours.

As a result of the analysis of the flame retardant E, it is understood that the main component is _{1- 1} in the formula (I) wherein R ₁ , R ₂ , R ₃ and R ₄ are 2-chloroethyl, Z ₁ and Z ₂ are methyl. Bis(2-chloroethoxy)phosphinyl]-1-methylethylbis(2-chloroethyl)phosphate.

As a result of GPC measurement, the compound of n=0 was 2.4 area%, the compound of n=1 was 30.4 area%, and the average degree of condensation (N) was 2.22.

In addition, the phosphorus content (P) is 13.8% by weight, the chlorine content (Cl) is 25.1% by weight, and the viscosity is 3850 mPa. s (25 ° C), acid value of 0.06 KOHmg / g.

[Comparative Example 1]

A ginseng (2-chloroethyl)phosphoric acid as the compound (a) was obtained in the same manner as in Example 1 except that 208 g (4.72 mol) of ethylene oxide was changed to 222 g (5.05 mol). A mixture of an ester and bis(2-chloroethyl)phosphorus chloride as compound (c) (1.03 mol and 0.95 mol, respectively). The active chlorine concentration of the reaction mixture was 6.9%.

Further, the obtained reaction mixture was kept at 40 ° C instead of 0 to 10 ° C, and it took 6 hours via the dropping funnel with respect to 1 mol of bis(2-chloroethyl)phosphorus chloride as the compound (c). Instead of adding 1.6 mol of acetone (64 g (1.10 mol)) as the compound (b) in 2 hours, it was allowed to react at the same temperature for 12 hours, and 71 g (0,73 mol) of a 35% aqueous hydrogen peroxide solution as an oxidizing agent was added. The flame retardant F was obtained in the same manner as in Example 1 except that the amount was changed to 98 g (1.01 mol).

As a result of analysis of the flame retardant F, it is understood that the main component is _{1- 1} in the formula (I) wherein R ₁ , R ₂ , R ₃ and R ₄ are 2-chloroethyl, Z ₁ and Z ₂ are methyl. Bis(2-chloroethoxy)phosphinyl]-1-methylethylbis(2-chloroethyl)phosphate.

As a result of GPC measurement, the compound of n=0 was 14.8 area%, the compound of n=1 was 59.3 area%, and the average degree of condensation (N) was 1.19.

In addition, the phosphorus content (P) is 13.0% by weight, the chlorine content (Cl) is 28.9% by weight, and the viscosity is 520 mPa. s (25 ° C), acid value of 0.03 KOHmg / g.

[Comparative Example 2]

A ginseng (2-chloroethyl)phosphoric acid as the compound (a) was obtained in the same manner as in Example 1 except that 208 g (4.72 mol) of ethylene oxide was changed to 215 g (4.90 mol). A mixture of an ester and bis(2-chloroethyl)phosphorus chloride as the compound (c) (0.90 mol and 1.10 mol, respectively). The active chlorine concentration of the reaction mixture was 8.0%.

Further, the obtained reaction mixture was kept at 40 ° C instead of 0 to 10 ° C, and it took 6 hours via the dropping funnel with respect to 1 mol of bis(2-chloroethyl)phosphorus chloride as the compound (c). Instead of adding 1.2 mol of acetone (77 g) of the compound (b) in an amount of 2 hours, it was allowed to react at the same temperature for 12 hours, and 87 g (0,89 mol) of a 35% aqueous hydrogen peroxide solution as an oxidizing agent was added. The flame retardant G was obtained in the same manner as in Example 1 except that the amount was changed to 65 g (0.67 mol).

As a result of analyzing the flame retardant G, it is found that the main component is R ₁ , R ₂ , R ₃ and R ₄ of the formula (I) is 2-chloroethyl, and Z ₁ and Z ₂ are methyl 1-[ Bis(2-chloroethoxy)phosphinyl]-1-methylethylbis(2-chloroethyl)phosphate.

As a result of GPC measurement, the compound of n=0 was 9.0 area%, the compound of n=1 was 54.8 area%, and the average degree of condensation (N) was 1.43.

In addition, the phosphorus content (P) is 13.4% by weight, the chlorine content (Cl) is 28.0% by weight, and the viscosity is 850 mPa. s (25 ° C), acid value of 0.04 KOHmg / g.

The results obtained are disclosed in Table 1.

Further, a well-known flame retardant (flame retardant H): a commercially available ginseng (2-chloroethyl) phosphate (manufactured by Supresta, product name: FYROL CEF) is used as a comparative reference example, and the results are disclosed in the table. 1.

This compound is a compound of the formula (I) wherein n is 0, R ₁ , R ₂ and R ₃ are 2-chloroethyl groups, the phosphorus content (P) is 10.8% by weight, the chlorine content (Cl) is 36.6 % by weight, and the viscosity is 45mPa. s (20 ° C).

From the results of Table 1, the reactions of Examples 1 to 5 in the step (1) are known. In the case of bis(2-chloroethyl)phosphorus chloride as the compound (c) relative to the ginseng (2-chloroethyl) phosphite 1 mol of the compound (a), 1.74 to 2.37 mol The ratio is further used at the same time as a ratio of 1.3 to 1.7 moles of acetone of the compound (b) relative to the bis(2-chloroethyl)phosphonium chloride 1 mol of the compound (c). The organophosphorus compound (I) has a content of a compound of the formula (I) wherein n = 0 (monomer type phosphate) is 0.5 to 2.4 area%, and an average degree of condensation (N) is 2.12 to 2.70.

On the other hand, in Comparative Examples 1 and 2, as a compound The ginseng (2-chloroethyl) phosphite 1 mole of (a) as the compound (c) has a ratio of bis(2-chloroethyl)phosphorous chloride of 0.92 and 1.22 moles, further simultaneously with respect to As the compound (c), bis(2-chloroethyl)phosphonium chloride 1 mole is used as the compound (b) in an acetone ratio of 1.1 mol and 1.2 mol, and the obtained organophosphorus compound is used. The content of the compound (monomeric phosphate) of n=0 in the formula (I) is as high as 14.8 area% and 9.0 area%, respectively. Therefore, the average condensation degree (N) of the organophosphorus compounds of Comparative Examples 1 and 2 was lower than that of Examples 1 to 5, and was 1.19 and 1.43, respectively.

In Comparative Example 1, the ratio of the ginseng (2-chloroethyl) phosphite as the compound (a) to the bis(2-chloroethyl)phosphorus chloride as the compound (c) was higher than that of the comparative example 2. Therefore, it is considered that the content of the monomeric phosphate having n=0 is large.

[Embodiment 6]

Using the flame retardant A obtained in Example 1, a polyurethane foam (foam) was produced by the following formulation and manufacturing method, and evaluated for flame retardancy, antifogging property, flame retardancy sustainability, and Phosphorus atom content maintenance rate.

(formula)

Polyol (manufactured by Mitsui Chemicals, Inc., trade name: ACTCOL T-3000) 100 parts

Oyster sauce (made by Toray Dow Corning Co., Ltd., trade name: SZ-584) 1.0 part

Amine catalyst

(Manufactured by Air Products and Chemicals, trade name: DABCO 33LV) 0.2 parts

(Manufactured by Air Products and Chemicals, trade name: DABCO BL-11) 0.05 parts

Tin-based catalyst

(manufactured by Air Products and Chemicals, trade name: DABCO T-9) 0.35 parts

Foaming agent (water) 4.3 parts

(methylene chloride) 8.0 parts

The number of parts required for the flame retardant (flame retardant A)

Isocyanate (toluene diisocyanate: TDI)

(Mitsui Chemical Co., Ltd., trade name: COSMONATE T-80 (80/20)) 58.2 parts

The above "parts" means parts by weight.

The number of added flame retardants was changed to 8, 10, 12 and 14 parts.

(Production method)

The polyol, the eucalyptus oil, the catalyst, the foaming agent and the flame retardant are blended in the above formula, and the mixture is stirred at a rotation speed of 3000 rpm for 1 minute using a stirrer. After homogeneous mixing, toluene diisocyanate was further added, and the mixture was stirred at a rotation speed of 3000 rpm for 5 to 7 seconds, and the contents were immediately poured into a corrugated box having a square (having a length of about 200 mm) cube (height of about 200 mm).

The foaming phenomenon occurs immediately and reaches a maximum volume in a few minutes. The obtained foam was allowed to stand in a furnace at 120 ° C for 30 minutes to be hardened. The obtained foam had a white soft connected bubble type bubble structure.

[Embodiment 7]

A foam was produced in the same manner as in Example 6 except that the flame retardant B obtained in Example 2 was used instead of the flame retardant A, and the flame retardancy, antifogging property, and flame retardancy were evaluated. Sex and phosphorus atom content maintenance rate.

[Comparative Example 3]

A foam was produced in the same manner as in Example 6 except that the flame retardant F obtained in Comparative Example 1 was used instead of the flame retardant A, and the flame retardancy, antifogging property, and flame retardancy durability were evaluated. And phosphorus atom content maintenance rate.

[Comparative Example 4]

A foam was produced in the same manner as in Example 6 except that the flame retardant H of the reference example was used instead of the flame retardant A, and the flame retardancy and the antifogging property were evaluated. Regarding the flame retardancy sustainability and the phosphorus atom content retention rate, since the evaluation of the antifogging property is poor, the test conditions cannot be withstood and the test cannot be performed.

(flame retardancy evaluation)

The sample was cut out from the obtained foam, and the burning test was performed under the following conditions.

Test method: FMVSS-302 method (test method for safety standard of automotive interior decoration products)

Horizontal burning test of polyurethane foam

Test conditions: The air permeability was adjusted to 200 ml/cm ² /sec. (The air permeability is measured in accordance with JIS K6400-7 B method.)

Sample: two samples with a thickness of 5mm and 13mm

Density is adjusted to 20 ~ 25kg / m ³ or so.

Qualified standard: The burning distance of 38mm or less is determined as qualified.

The results obtained are disclosed in Table 2.

(anti-fog evaluation)

The sample was cut out from the obtained foam, and the atomization test was performed under the following conditions.

Test conditions: A windshield atomization tester (manufactured by SUGA Test Machine Co., Ltd.) was used, and a sample of a polyurethane foam (having a diameter of 80 mm and a thickness of 10 mm) was placed under the container at 100 ° C. The sample was heated for 16 hours, and the amount of the glass plate adhered to the upper portion of the container by the scattering material generated from the sample was measured, and this was used as the glass adhesion amount (mg).

Sample: One sample, the flame retardant is added in 8 parts.

The results obtained are disclosed in Table 3.

From the results of Table 2, it is known that Example 6 containing flame retardant A and The polyurethane foam of Example 7 having the flame retardant B has a very good flame retardancy as compared with Comparative Example 4 in which the amount of the flame retardant H is increased and contains the conventional flame retardant H. In Comparative Example 3 of the flame retardant F of the condensation type flame retardant, although there was slightly good flame retardancy, there was no significant difference.

However, as is apparent from the results of Table 3, in the polyurethane foams of Examples 6 and 7, the glass adhesion amount, that is, the volatile component was significantly reduced to 1/4 or less, and the antifogging property was compared with Comparative Example 3. Excellent.

(flame retardant sustainability assessment)

The sample was cut out from the obtained foam, and the flame retardancy durability test was performed under the following conditions.

The sample was placed in an aging tester set at a temperature of 150 ° C, and after 2, 4, 6 and 8 hours of exposure, the flame retardancy was evaluated in the same manner as the flame resistance evaluation.

In addition, the test was performed in the same manner for the reference sample having an exposure time of 0 hours.

The results obtained are disclosed in Table 4 and Figure 1.

As is apparent from the results of Table 4 and FIG. 1, the embodiment containing the flame retardant A 6 and the polyurethane foam of Example 7 containing the flame retardant B was exposed to a high temperature for 8 hours, and the burning distance was slightly longer, and On the other hand, the polyurethane foam of Comparative Example 3 containing the flame retardant F of the conventional condensed flame retardant was exposed to high temperature for 8 hours, and the burning distance was before exposure (0 hour of exposure time). 2 times. That is, the flame retardants A and B of the present invention are more excellent in flame retardancy than those of the flame retardant F, and are excellent in flame retardancy.

(Assessment of phosphorus atom content maintenance rate)

The sample was cut out from the obtained foam, and the phosphorus atom content retention ratio was evaluated under the following conditions.

The sample was placed in an aging tester set at a temperature of 80 ° C for 14 days, and the phosphorus atom content in the sample after exposure for 3 days, 7 days, and 14 days after exposure at a high temperature was measured in accordance with ASTM D 1091.

Similarly, the sample was placed in an aging tester set at a temperature of 100 ° C for 7 days, and the phosphorus atom content in the sample after exposure for 1 day, 3 days, and 7 days after exposure at a high temperature was measured in accordance with ASTM D 1091.

In addition, the unexposed reference sample was also measured in the same manner, and the obtained phosphorus atom content was set to 100%, and the ratio of the phosphorus atom content in the sample after exposure at a high temperature was calculated, and this was used as a phosphorus atom. Content maintenance rate.

The results obtained are disclosed in Table 5 and Figure 2.

As is apparent from the results of Table 5 and FIG. 2, the embodiment containing the flame retardant A 6 and the polyurethane foam of Example 7 containing the flame retardant B, even if exposed to a high temperature at a temperature of 80 ° C for a long period of time, although the phosphorus atom content retention rate is slightly lowered, the 14-day exposure is maintained. On the other hand, the flame retardant F contained in the polyurethane foam of Comparative Example 3 is a conventional condensation type flame retardant, and the phosphorus atom content retention rate after 14 days of exposure. Reduced to 86%. That is, the flame retardants A and B of the present invention have a very low scattering of phosphorus atoms and a high maintenance ratio as compared with the flame retardant F.

In addition, the flame retardants A and B exposed at 100 ° C for 7 days have a phosphorus atom content retention ratio of 82% or more, and have a higher phosphorus atom content retention ratio as compared with 71% of the flame retardant F. .

In the case of the flame retardant F, when it is exposed to high temperature for a long time, it is contained The monomeric phosphate component volatilizes or scatters and disappears. As a result, the content of phosphorus atoms in the foam is reduced, and the flame retardancy is considered to be lowered.

On the other hand, in the flame retardants A and B of the present invention, since the content of the monomeric phosphate component of the volatile component is extremely small compared with the flame retardant F, the amount of phosphorus atoms lost by the foam is also very small. It is considered to have a high phosphorus atom content retention rate and excellent flame retardancy persistence.

From the above results, it is understood that the flame retardant of the present invention and the flame-retardant resin composition containing the same exhibit excellent flame retardancy among the required conditions, and the change in sustainability is small in time. Excellent antifogging property and low volatile components.

Claims (10)

A flame retardant for a resin containing an organophosphorus compound represented by the general formula (I): (wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently an alkyl group having 1 to 8 carbon atoms or a haloalkyl group, and Z ₁ and Z ₂ are each independently a hydrogen atom, a methyl group or an ethyl group; n is 0 to 10), and when the organophosphorus compound is measured by gel permeation chromatography (GPC), the content of the compound of n=0 in the above formula (I) is 0.1 to 3.0 area%, and The average condensation degree (N) calculated from the content of each compound of n=0 to 10 in the formula (I) is from 1.5 to 3.5. The flame retardant for a resin according to claim 1, wherein when the organophosphorus compound is measured by GPC, the content of the compound of n=1 in the above formula (I) is 10 to 50% by area. The flame retardant for a resin according to claim 1, wherein the average degree of condensation (N) in the above formula (I) is from 1.8 to 3.0. A flame-retardant resin composition comprising the flame retardant for a resin according to claim 1 and a resin. The flame-retardant resin composition of claim 4, wherein the resin is selected from the group consisting of polyurethane resin, acrylic resin, phenol resin, epoxy resin, Resin of vinyl chloride resin, polyamide resin, polyester resin, unsaturated polyester resin, styrene resin and synthetic rubber. The flame-retardant resin composition of claim 5, wherein the polyurethane resin is a polyurethane foam. The flame-retardant resin composition of claim 4, which comprises 1 to 40 parts by weight of the flame retardant for the resin, based on 100 parts by weight of the resin. A method for producing an organophosphorus compound, comprising the steps of: (1) a compound represented by the formula (a), a compound (b) represented by the formula (b), and a formula (a) c) the compound (c) represented by the above compound (a) is at a ratio of 1.5 to 3.5 moles relative to the compound (a), and further to the aforementioned compound (c) The compound (b) is a ratio of 1.3 to 2.0 mol, and is reacted at a temperature of -20 to 60 ° C to obtain a compound (d) represented by the formula (d): (wherein R ₁ and R _{2 have the} same meaning as in the formula (I), and R ₅ is an alkyl group having 1 to 8 carbon atoms or a haloalkyl group), (wherein, Z ₁ and Z _{2 are} synonymous with the formula (I)), (wherein R ₃ and R _{4 have the} same meaning as in the formula (I), and X is a halogen atom), Wherein R ₁ , R ₂ , R ₃ , R ₄ , Z ₁ , Z ₂ and n are synonymous with the formula (I); and the step (2) is obtained by the oxidizing agent obtained in the above step (1) The compound (d) is oxidized to obtain an organophosphorus compound represented by the above formula (I). When the organophosphorus compound is measured by GPC, the content of the compound of n=0 in the above formula (I) is 0.1 to 3.0 area%. And the average degree of condensation (N) calculated from the content of each compound of n=0 to 10 in the above formula (I) is from 1.5 to 3.5. The method for producing an organophosphorus compound according to claim 8, wherein when the organophosphorus compound is measured by GPC, the content of the compound of n = 1 in the above formula (I) is from 10 to 50% by area. The method for producing an organophosphorus compound according to claim 8, wherein the average degree of condensation (N) in the above formula (I) is from 1.8 to 3.0.